Preparation of alpha-aminonitriles



United States Patent 3,503,995 PREPARATION OF ALPHA-AMINONITRILES EllisK. Fields, Chicago, Ill., assignor to Standard Oil Company, Chicago,Ill., a corporation of Indiana No Drawing. Original application Apr. 30,1965, Ser. No. 452,331. Divided and this application Nov. 30, 1966, Ser.No. 620,571

Int. Cl. 'C07c 121/04 U.S. Cl. 260-3432 3 Claims ABSTRACT OF THEDISCLOSURE Alpha-aminonitriles are obtained from the ozonolysis of anorganic compound containing at least one nonaromatic carbon to carbondouble bond in the presence of hydrogen cyanide and ammonia in a liquidreaction medium.

This application is a division of application Ser. No. 452,331, filedApr. 30, 1965, which in turn is a icontinuation-in-part of applicationSer. No. 393,391, filed Aug. 31, 1964, now abandoned.

This invention relates to the ozonization of organic compounds. Moreparticularly, it relates to liquid phase ozonization of organiccompounds containing at least one carbon to carbon double bond in thepresence of hydrogen cyanide and to hydroxy-substituted oramino-substituted nitriles formed from such compounds.

Recent developments of simplified techniques for ozone preparation makeozone increasingly an important oxidant in large-scale oxidationprocesses and diminish rapidly the traditional ill-fame associated withits hazards and cost. The key for the elfective application of ozonelies inavoiding ozonite accumulation or isolation prior to thesubsequent decomposition by further oxidation, reduction, or solvolysis.Ideally, the highly reactive and unstable ozonide should be convertedquickly and simply to be desired product.

The reaction of ozone with unsaturated organic compounds has been knownfor many years, and has been the subject of extensive study. The artrelating thereto has been collected and analyzed by Long in TheOzonization Reaction, Chemical Reviews, 27, 437-493 (1940), and in amore recent extensive review by Bailey, Chemical Reviews, 58, 925(1958).

I have discovered that liquid phase ozonization of organic compoundscontaining at least one carbon to carbon double bond under basicreaction conditions in a liquid reaction medium containing at least twomoles of hydrogen cyanide per mole of said compound yields hydroxynitriles as the primary ozonolysis products. Further, that aminonitriles are the primary products of the reaction when the liquidreaction medium also contains ammonia or an ammonia generating compound.The primary products of the reaction can be recovered per se or as theacetates thereof from the reaction mixture; or, if desired, be convertedin situ to their corresponding hydroxyor amino-substituted acids.

The method of the invention comprises ozonizing an organic compoundcontaining at least one carbon to carbon double bond with ozone underbasic reaction conditions in a liquid reaction medium containing atleast two moles of hydrogen cyanide per mole of said compound and from Oto 5 moles of ammonia per mole of said hydrogen cyanide. It is essentialthat the liquid reaction medium be maintained basic during the reactionwith ozone. The reaction temperature is not critical and may range from--60 C. to +25 C. Preferably, the temperature is maintained from C. toC. to avoid loss of hydrogen cyanide. The reaction time is dependentupon rate of addition of ozone to the reaction 'ice medium. Besideshydrogen cyanide, any suitable cyanide generating compound can be used.Potassium cyanide or sodium cyanide are preferred reactants to providehydrogen cyanide and maintain the requisite basicity during thereaction. Because ozone reacts with the cyanide, amounts of thesereactants in excess of the stoichiometric proportions required to reactwith the double bond should be used.

The liquid reaction system can be homogeneous or heterogeneous,depending upon the choice of liquid for the reaction medium. Maximumconversion is obtained in an aqueous (heterogeneous) reaction systemcontaining a stable emulsifier such as Brij 30 (a commercialpolyoxyethylene lauryl alcohol). Other liquids that are suitable areanhydrous ammonia, concentrated ammonium hydroxide, alkanols, ethers,low molecular weight paraffinic hydrocarbons, such as butane, pentane,hexane, heptane, and low molecular weight chlorinated paraffins, such asmethylene chloride, carbon tetrachloride, and chloroform. The onlylimitation is that the liquid or solvent be inert to ozone.

Any organic compound containing at least one carbon to carbon doublebond susceptible to cleavage with ozone can be treated in accordancewith the present invention to form valuable new chemical compoundsuseful per se or as chemical intermediates. Olefins can be converted tohydroxy nitriles (cyanohydrins) or amino nitriles or to theircorresponding carboxylic acids. Cycloolefins can be cleaved to form thecorresponding dihydroxy or diamino dinitriles or dicarboxylic acidscontaining two more carbon atoms. Lactones or lactams are obtained fromaryl fused cycloolefins, such as indene and acenaphthylene. Illustrativeof such compounds are: (A) substituted and unsubstituted aromatichydrocarbons, such as benzene, naphthalene, anthracene, phenanthrene,chrysene, rubrene, and coronene; (B) homoand co-polymers ofpolymerizable compounds, such as ethylene, propylene, isobutylene,styrene, acrylates, etc.; (C) aryl olefins, such as styrene, stilbene,allylbenzene, and divinylbenzene; (D) heterocyclic olefins, such as 2-and 4-vinylpyridine, vinyl quinoline, and 1,2-dipyridyl ethylene; (E)olefins containing substituents including (1) hydroxy, such as allylalcohol, l-butene- 4-ol, and oleyl alcohol; (2) alkoxy, such as allylmethyl ether, crotyl butyl ether, and phenyl allyl ether; (3) keto, suchas methyl vinyl ketone, l-cyclohexene-S-one, and benzylidene acetone;(4) carboxy, carbalkoxy, and carboxamido, such as oleic acid, crotonicacid, and cinnamic acid and their esters and amides; (5) olefinicdicarboxylic anhydrides, such as propenyl succinic anhydride, andgenerally the anhydrides from olefins and maleic anhydride, such asdodecenylsuccinic anhydride; (6) acyl-amino, such as N-allylacetarnideand N-oleylbenzamide; and (7) halo, such as allyl chloride, pbromostyrene, and hexachloronorbornylbutene; (F) sulfone, such assulfolene and divinyl sulfone; (G) alicyclic olefins and terpenes, suchas alphaand beta-pinene, camphene, and dipentene; and (H) steroids, suchas cholesterol, cholestenone, and ergosterol.

The following examples are for illustrative purposes and are not meantto limit the invention in any way. In the examples, the temperatures arein degrees centigrade. The ozone was produced by a commercial ozonatorin a concentration of 2.83.0 Wt. percent in oxygen. The gas mixture ofozone and oxygen was introduced into the liquid reaction medium in astirred reaction, and the vent gases passed through a neutral potassiumiodide trap. Ozone introduction was stopped when the concentration ofozone increased in the vent gases as indicated by the color change inthe potassium iodide trap. The usual analytical techniques of elementalanalysis, infrared and mass spectroscopy, melting point and/ or mixturemelting points were used for product identification.

EXAMPLE 1 An emulsion of 37.5 g. (0.5 mole) of potassium cyanide, 250ml. water, 0.5 g. Brij 30, and 37.3 g. (0.2 mole of 90%) cyclododecenewas established by rapid mixing in a 1 liter flask. At 33.7 ml. (0.4mole) concentrated hydrochloric acid was added and then 14.4 g. (0.3mole)ozone was passed into the emulsion in 132 minutes. Thereafter, anadditional 15 ml. concentrated hydrochloric acid was added to induceseparation of the emulsion, which took one hour at 25 The semi-solidorganic layer was separated from the aqueous phase and refluxed for 3hours with 50 ml. ethanol, 20 ml. hydrochloric acid, and 200 ml. water.The mixture was evaporated to dryness on a steam bath, and the residuewas dissolved in aqueous sodium hydroxide. The alkaline solution wasfiltered, and the filtrate acidified. The precipitate was crystallizedfrom boiling water to give 19.7 g. (34 mole percent) of White crystalsmelting at 123-5 and identified as 1,12 dihydroxydodecane 1,12dicarflaoxylic acid.

Analysis.Calculated (percent): C, 57.9; H, 9.0; neutral equivalent 145.Found (percent): C, 57.6; H, 9.3; neutral equivalent 145.

.EXAMPLE 2 A homogeneous solution of 0.2 mole cyclooctene and 0.6 molehydrogen cyanide in 250 ml. ethanol containing 1 g. potassium hydroxidewas ozonized at with 0.3 mole ozone. Excess hydrogen cyanide was removedby blowing with air. The alcohol solution was refluxed with 50 ml.concentrated hydrochloric acid for 2 hours and evaporated. Ether wasadded, and the ether solution was extracted with base. Acidification ofthe alkaline extract gave 6.1 g. (13 mole percent) 2,9-dihydroxyaebacicacid.

EXAMPLE 3 An emulsion of 49.3 g. (1 mole) sodium cyanide, 250 ml. water,22 g. (0.2 mole) cyclooctene, 0.5 g. Brij 30, and 37.2 ml. (0.65 mole)acetic acid was ozonized at 5 with 14.4 g. (0.3 mole) ozone. Thereafter,80 ml. concentrated hydrochloric acid was added to'the mixture, andmixture was warmed until emulsion broke. Ether was added, and ethersolution extracted with potassium hydroxide. Acidification of thealkaline extract gave 20 g. (43 mole percent) 2,9-dihydroxycebacic acid,M.P. 134.

Analysis.Calculated (percent): C, 51.3; H, 7.7; neutral equivalent, 117.Found (percent): C, 51.4; H, 7.5; neutral equivalent, 118.

EXAMPLE 4 An emulsion of 65.1 g. (1 mole) potassium cyanide, 250 ml.water, 0.5 g. Brij 30, 22 g. (0.2 mole) cyclooctene, and 51.5 ml. (0.4mole) acetic acid was ozonized at 20 with 14.4 g. (0.3 mole) ozone.Mixture was warmed to 80 and held for 0.5 hour, and cooled. To thecooled mixture was added 25 g. sodium chloride and 250 ml. ether formingthree layers. Middle layer was filtered through Celite giving 20.5 g.(52 mole percent) 1,8-dihydroxy-l,8-dicyanooctane.

Analysis-Calculated (percent): C, 61.2; H, 8.2; N, 14.3. Found(percent): C, 60.7; H, 8.0; N, 14.7.

EXAMPLE 5 An emulsion of 49.3 g. (1 mole) sodium cyanide, 250 ml. Water,23.2 g. (0.2 mole) indene, 0.5 g. Brij 30, and 37.2 ml. (0.65 mole)acetic acid was ozonized at 5 with 14.4 g. (0.3 mole) ozone. Reactionmixture ex tracted with ether. Extraction of the ether solution withpotassium hydroxide, and acidification of the filtrate gave 32 molepercent of white solid M.P. 152-154 identified as1oxo-isochroman-3-carboxylic acid Analysis.Calculated (percent): C,62.4; H, 4.2; neutral equivalent, 192. Found (percent): G, 62.2; H, 4.2;neutral equivalent, 191.

EXAMPLE 6 An emulsion of 30.4 g. (0.2 mole) acenaphthylene in 250 ml.ether, 245 g. (0.5 mole) sodium cyanide, 200 ml. water, and 0.5 g. Brij30 was treated at 0 with 25.74 ml. (0.45 mole) acetic acid, thenozonized with 14.4 g. (0.3 mole) ozone over 132 minutes. The mixture waswarmed at for 0.5 hour (after the ether had boiled 01f), cooled andmixed with 350 ml. ether. The ether layer was filtered from a brownsolid, washed with water, and evaporated. The residue was refluxed with50 ml. hydrochloric acid for 2 hours, then evaporated on the steam bath.This residue was dissolved in excess 5% potassium hydroxide, filtered,and acidified, giving 15.5 g. naphthalide-3-carboxylic acid (34 molepercent) melting at 208-210 after 2 crystallizations from water.

Analysis.--Calculated for C H O (percent): C, 68.4; H, 3.5; neutralequivalent, 228. Found (percent): C, 68.4; H, 4.0; neutral equivalent,227.

EXAMPLE 7 An emulsion of 49 g. (1 mole) sodium cyanide, 300 ml. water,53.5 g. (1 mole) ammonium chloride, 20 ml. concentrated ammoniumhydroxide, 0.5 g. Brij 30, and 37.3 g. (0.2 mole of cyclododecene wasozonized with 14.4 g. (0.3 mole) ozone at 5 over a period of 132minutes. The ozonized mixture was heated at 80 for 0.5 hour, and thenwas refluxed 3 hours with 300 ml. concentrated hydrochloric acid. Themixture was filtered, and the cooled filtrate was brought to pH 8 by theaddition of ammonium hydroxide. The solid precipitate was filtered,washed with water, and dried; it weighed 7.1 g. (12 mole percent), witha M.P. 440, and was identified as 1,12-diaminododecane-1,IZ-dicarboxylicacid.

Analysis.Calculated (percent): C, 58.3; H, 9.7; N, 9.7. Found (percent):C, 58.0; H, 9.8; N, 9.6.

EXAMPLE 8 An emulsion of 65 g. (1 mole) potassium cyanide, 200 ml.water, 50.4 g. (0.2 mole) l-octadecene, 275 ml. pentane, 0.5 g. Brij 30,and 37.2 ml. (0.65 mole) acetic was ozonized at 0 with 14.4 g. (0.3mole) ozone for 132 minutes. The mixture was blown with air at 25 for 30minutes to remove hydrogen cyanide; then 65 ml. concentratedhydrochloric acid added, and the mixture warmed at 80 for 20 minutes.When it was cooled, 2- hydroxystearonitrile separated as a solid upperlayer. This was crystallized twice from hexane to give 50.6 g. (89 molepercent) of white crystals melting at 45-47".

Analysis.Calculated (percent): C, 76.3; H, 13.1; N, 4.9. Found(percent): C, 76.0; H, 12.9; N, 4.7.

A portion of the Z-hydroxystearonitrile, 2.83 g. (0.01 mole) was heatedat in a bomb with 5 ml. concentrated ammonium hydroxide and 2 g.ammonium carbonate. The product was refluxed 3 hours with excesshydrochloric acid, cooled, and filtered; the solid was refluxed 2 hourswith 5 ml, ammonium hydroxide. The amino acid, Z-amino stearic acid, wascollected on a filter, washed, dried, and crystallized from acetic acidwith a little charcoal. It weighed 2.15 g. (72 mole percent) and meltedat 224-5 dec. (literature melting point is 223).

Analysis.-Calculated (percent): C, 72.2; H, 12.4; N, 4.7. Found(percent): C, 71.9; H, 12.2; N, 4.5.

Another portion of the 2-hydroxystearonitrile of this example, 5.66 g.,was refluxed for 6 hours with 20 ml. benzene and 25 ml. concentratedhydrochloric acid, the benzene boiled oif, and the mixture cooled, andfiltered. Solids recrystallized from chloroform gave 6.1 g. (89 molepercent) of 2-hydroxystearic acid, M.P. 912. Mixture melting point withauthentic 2-hydroxystearic acid, 9092.

A 2 g. portion of the Z-hydroxystearonitrile of this example was warmedwith 6 ml. of concentrated hydrochloric acid on the steam bath forminutes. Recrystallization from ethanol of the filtered and dried solidgave 2 g. (95%) of 2-hydroxystearamide, M.P. 145 (literature meltingpoint is 148).

EXAMPLE 9 A solution of 32.8 (0.2 mole) 5-norbornene-2,3-dicarboxylicanhydride in 10 g. sodium hydroxide and 150 ml. water was mixed with45.6 g. (0.7 mole) potassium cyanide in 100 ml. water and 37.2 ml. (0.65mole) acetic acid; the mixture was ozonized at 0 with 19.6 g. (0.4 mole)ozone. The ozonized mixture was stirred at 25 for 30 minutes, treatedwith 200 ml. concentrated hydrochloric acid, and evaporated to drynesson steam bath. The residue was ground and extracted in Soxhlet apparatusfor 48 hours with ether. The ether was vacuum evaporated at 60, giving4.6 g. viscous products that did not crystallize. Product was identifiedas the lactone of 1,2- dicarboxycyclopentane-3,5-diglycolic acid.

Analysis.Calculated (percent): C, 45.8; H, 4.2; saponificationequivalent, 72. Found (percent): C, 45.4; H, 4.4; saponificationequivalent, 71.

EXAMPLE 10 An emulsion of 32.4 g. (0.2 mole) 1,5,9-cyclod0decatriene(10% cis, trans, trans; 90% all trans) in 150 ml. of aqueous hydrogencyanide (0.4 mole) and 0.1 mole potassium cyanide was ozonized at 0 with14.4 g. (0.3 mole) ozone. After being extracted with ether andacetylated with acetic anhydride, the product distilled at 1924 and 0.3mm., giving 13.3 g. (20 mole percent) of 1,12-dicyanol-l,l2-diacetoxydodecadiene-4,8

Analysis.-Ca1culated for C H N O (percent): C, 65.0; H, 7.2; N, 8.4.Found (percent): C, 64.7; H, 7.6; N, 8.1.

The compound was thermally stable at 250. Its molecular weight:calculated, 332; found (by mass spectrometry), 332.

EXAMPLE 11 An emulsion of 31.72 ml. (0.2 mole) of alpha-pinene in 150ml. water containing 0.4 mole of hydrogen cyanide, 0.1 mole of potassiumcyanide, and 0.5 g. Brij 30 was ozonized at 0 with 14.4 g. (0.3 mole)ozone. The product was extracted with ether, acetylated with aceticanhydride, and distilled. The product recovered was 1,1-

dimethyl 2 acetylcyclobutane-4-(Z-acetoxy) propionitrile having aboiling point of 173 at 1 mm.

Analysis.Calculated for C H NO (percent): C, 65.8; H, 8.0; N, 5.9. Found(percent): C, 65.9; H, 8.4; N, 5.7.

The mass spectrum gave the molecular weight as 237; calculated, 237.

EXAMPLE 12 An emulsion of 33.6 (0.2 mole) l-dodecene in 150 ml.concentrated ammonium hydroxide containing 0.4 mole of hydrogen cyanideand 0.5 Brij 30 was ozonized at 5 with 14.4 g. (0.3 mole) ozone. Afterbeing extracted with ether and acetylated, it gave 10.5 g. (22 molepercent) of Z-acetaminolauronitrile, B 187-190, M.P. 60.

Analysis.Calculated for C H H O (percent): C, 70.6; H, 10.9; N, 11.8.Found (percent): C, 70.3; H, 11.1;N, 11.6.

EXAMPLE 13 An emulsion of 33.6 g. (0.2 mole) l-dodecene in 150 ml. watercontaining 0.4 mole hydrogen cyanide and 0.1 mole potassium cyanide wasozonized with 14.4 g. (0.3 mole) ozone at 0. After being extracted withether and acetylated, the product distilled at 124-7 and 0.5 mm., giving19.6 g. (41 mole percent), of 2-acetoxylauronitrile.

Analysis.Calculated for C H NO (percent): C, 70.3; H, 10.5; N, 5.9.Found (percent): C, 70.6; H, 10.8; N, 6.0.

EXAMPLE v14 A solution of 22 g. (0.2 mole) cyclooctene in 250 ml. ethercontaining 0.5 mole hydrogen cyanide, and 1 g. sodium cyanide in 2 ml.water was ozonized with 14.4 g. (0.3 mole) ozone at 0, then acetylated,and distilled. The product, 19 g. (34 mole percent) B 190193, was2,9-diacetoxysebaconitrile.

Analysis.--Calculated for C H N O (percent): C, 60.0; H, 7.1; N, 10.0.Found (percent): C, 59.8; H, 7.3; N, 9.8.

Molecular weight: calculated, 280. Found (mass spectrum), 280.

EXAMPLE 16 A mixture of 38.6 g. (0.1 mole) of cholesterol, and 0.4 moleof hydrogen cyanide in 250 ml. ether, and 2 g. of sodium cyanide in 4ml, water was ozonized at 20 with 14.4 g. (0.3 mole) ozone. Concentratedhydrochloric acid, 4 ml., was added: the ether layer was separated, andevaporated on the steam bath, giving 40.8 g. yellow solid that melted at132 with decomposition.

Analysis.Calculated for C H NO (percent): C, 75.5; H, 10.6; N, 3.1.Found (percent): C, 74.7; H,

The product is CH3 CH3 CH3 (EH-(CH2)3--CH (1H2 (llHz GHOH as shown byits analysis and infrared spectrum. The band at 1690 cm.- is the ketonecarbonyl; OH band is at 3480 cmr and 2 C,OH bands, at 1070 cm:- and 1005cm.- show the two different OH groups.

EXAMPLE 17 A solution of 72.8 g. (0.2 mole) methyl abietate in 350 ml.ether containing 1.37 moles hydrogen cyanide and ml. (0.1 mole)piperidine was ozonized at 0 with 28.8 g. (0.6 mole) ozone. Concentratedhydrochloric acid, -ml. was added: the ether layer was dried, andevaporated, giving 89.2 g. viscous cyanohydrin'of structure:

11 0 C 0 OMG CH2-CHOHOH OH 2 CH3 Analysis.Calculated for C H NO(percent): C, 70.6; H, 8.6; N, 3.7. Found (percent): C, 71.4; H, 9.4; N,4.0.

EXAMPLE 18 An emulsion of 19.2 g. (0.2 mole) of l-methylcyclohex ened,24.5 g. (0.5 mole) of sodium cyanide, 150 ml. water, and 0.5 g. Brij 30was treated at 10 with 33.7 ml. (0.4 mole) of concentrated hydrochloricacid, then ozonized with 14.4 g. (0.3 mole) ozone at 20. Ether,

250 ml., and g. sodium chloride were added; the 4 other layer wasseparated, dried, and treated with 75 m1.

of acetic anhydride and 1 ml. of concentrated hydrochloric acid. Afterbeing heated on the steam bath for minutes, it was evaporated in a Rincoevaporator at 40 and 0-2 mm., to give 17 g. light yellow, syrupy productthat analyzed 59.2% C; 7.7% H; and 9.1% N.

Calculated for oHa- (OH2)4CHCN (percent): C, 60.9; H, 7.6; N, 7.1.

Calculated for UN CH;%(CH2)4CHCN CH OAe o OH3(I% symmetrical bendingband at 1360 GEL-1, and the 8 C-OH stretching band for a tertiaryalcohol at 1220 cm.

EXAMPLE 19 An emulsion of 16.8 g. (0.2 mole) of cyclohexene, 24.5 g.(0.5 mole) of sodium cyanide, 150 ml. water, 0.5 g. Brij 30, and 33.7 g.(0.4 mole) concentrated hydrochloric acid was ozonized at 0 with 14.4 g.(0.3 mole) ozone. Ether and sodium chloride were added, the ether layerwas acetylated as in Example 18, and distilled, giving 10.1 g. (20 molepercent) of 2,6-diacetoxysuberonitrile.

Analysis.-Calculated for C H N O (percent): C, 57.2; H, 6.3; N, 11.1.Found (percent): C, 57.2; H, 6.7; N, 10.9.

The molecular weight, 252, was deduced from the mass spectrum; a peak at253 was the protonated parent peak, arising from a bimolecular reaction,as shown by its pressure dependence.

EXAMPLE 20 An emulsion of 44.8 g. (0.2 mole) l-hexadecene in 200 ml.pentane and 150 ml. water containing 0.4 mole hydrogen cyanide, 0.1 molesodium cyanide, and 0.5 g. Brij 30 was ozonized at 0 with 14.4 g. (0.3mole) ozone. After 10 ml. concentrated hydrochloric acid was added, themixture was air blown at 50 for 30 minutes to remove pentane and excesshydrogen cyanide, then chilled to 0. The precipitate was filtered, anddried, giving 39.5 g. (78 mole percent) of 2-hydroxypalmitonitrile. Aportion was heated with 2 X its weight of concentrated bydrochloric acidat 100 for 5 minutes and gave a quantitative yield ofZ-hydroxypalmitamide, M.P. 148 (literature melting point is 149.5

A portion of the Z-hydroxypalmitamide was converted toN-n-butyl-Z-hydroxypalmitamide in quantitative yield by refluxing with 2times its weight of n-butylamine for 20 hours with ammonia evolution.The solid was recrystallized from hexane, and melted at 98.

Analysis.Calculated for C H NO (present): C, 73.4; H, 12.5; N, 4.3.Found (percent): C, 73.2; H, 12.4; N, 4.6.

EXAMPLE 21 An emulsion of l-hexadecene in 200 ml. pentane and 200 m1.aqueous solution containing 56.6 ml. concentrated ammonium hydroxide,0.4 mole hydrogen cyanide, and 0.1 mole sodium cyanide was ozonized with14.4 g. (0.3 mole) ozone at 0. The mixture was heated for 30 minutes at80 with air blowing; ml. concentrated hydrochloric acid was added, andheating continued at 80 for 5 minutes. The mixture was cooled to 10; thesolid top layer was filtered, washed, and dried. 41.3 g. (71 molepercent) of 2-aminopalmitonitrile hydrochloride, melting at 94 aftercrystallization from hexane, was recovered.

Analysis.Calculated for C H N C1 (percent): C, 66.6; H, 11.4; N, 9.7;C1, 12.3. Found (percent): C, 66.3; H, 11.1; N, 9.4;C1, 11.9.

EXAMPLE 22 A mixture of 59.3 g. (0.2 mole) methyl oleate in 250 m1.ether containing 0.5 mole of hydrogen cyanide, and 2 g. (0.04 mole) ofsodium cyanide in 4 ml. water was ozonized at 0 with 14.4 g. (0.3 mole)ozone. After being treated with 8 ml. concentrated hydrochloric acid,the mixture was blown with air at 25 for 30 minutes to remove excesshydrogen cyanide. Acetic anhydride, 95.2 ml. (1 mole), was added, themixture heated at 100 for 30 minutes, then distilled. At 75-7 and 0.2mm., 18.15 g. (43 mole percent) of 2-acetoxycapric nitrile distilled.

Analysis.-Calcu1ated for C H NO (percent): C, 70.5; H, 10.0; N, 6.6.Found (percent): C, 70.7; H, 10.3; N, 6.4.

At 156-160 and 1.2 mm., 16.8 g. (33 mole percent) of methyl9'-cyano-9-acetoxy pelargonate distilled.

Analysis.-Calculated for C H NO (percent): C, $1.2; H, 8.2; N, 5.5.Found (percent): C, 61.6; H, 8.5;

The reaction is A solution of 36 g. (0.2 mole) trans-stilbene in 500 ml.ether was emulsified in 120 ml. aqueous hydrogen cyanide solutioncontaining 0.5 mole of hydrogen cyanide and 5 g. (0.1 mole) sodiumcyanide with 0.5 g. Brij 30. The mixture was ozonized at 15 with 14.4 g.(0.3 mole) ozone, then acidified with 10 ml. concentrated hydrochloricacid. The ether layer was extracted with 10% aqueous sodium hydroxide toremove 0.7 g, of benzoic acid, then evaporated on the steam bath, andchilled; 5.1 g. stilbene crystallized and was filtered 015.. Thefiltrate was acetylated with 20.4 g. (0.2 mole) of acetic anhydride and0.5 ml. concentrated hydrochloric acid at 100 for 1 hour, thendistilled, giving 29.7 g. (49 mole percent) of mandelonitrile acetateboiling at 120125 and 2 mm. The mass spectrum showed the correctmolecular weight, 175.

EXAMPLE 24 A mixture of 23.6 g. (0.2 mole) allylbenzene, 96 ml. (0.8mole) aqueous hydrogen cyanide, 90.6 ml. (1.6 mole) concentratedammonium hydroxide, and 0.25 g. Brij 30 was ozonized at with 14.4 g.(0.3 mole) ozone. Another 02 mole aqueous hydrogen cyanide and 22.6 ml.(0.4 mole) concentrated ammonium hydroxide were added, and the stirringcontinued at 20 for 3 hours. The mixture was acidified with 240 ml.concentrated hydrochloric acid, and evaporated to dryness on the steambath. The residuewas extracted with 100 ml. methanol at 20; the methanolwas filtered, and treated with 20 ml. aniline, The solid was collected,and dried, giving 6.6 g. dl-phenylalanine, melting at 263 aftercrystallization from water (literature melting point is 263- EXAMPLE 25An emulsion of 94 g. (1 mole) norbornylene in 100 ml. hexane and 200 ml.water containing 1.5 moles hydrogen cyanide, 1 g. Brij 30, and 0.2 molesodium cyanide was ozonized at 0 with 1.2 moles ozone. After beingextracted with ether and acetylated with aceti anhydride, the productwas evaporated in a Rotavapor evaporator, giving 54.5 g. viscous yellowdicyanohydrin diacetate OAc I OH-CN Analysis.--Calculated for C H N O(percent): C, 59.1; H, 6.1; N, 10.6; molecular weight, 264. Found(percent): C, 59.8; H, 6.9; N, 9.9; molecular weight (mass spectrum)264.

EXAMPLE 26 A mixture of 45.1 g. (0.44 mole) 1,5-hexadiene, 80.8 ml. (0.5mole) hexachlorocyclopentadiene, and 1 g. hydroquinone was heated atreflux for 18 hours, then at 130 for 2 hours. Distillation of themixture gave 72 g. (46 mole percent) of the adduct,l-hexachloronorb0rnylbutene-4,

cl '4 cl WQHYCMCH Cl Ci boiling at 123-125 at 1 mm.

all

cl cl Analysis.-- Calculated for C H NOCI (percent); C, 34.4; H, 2.3; N,3.6; CI, 55.4. Found (percent): C, 35.1; H, 2.5; N, 3.2; CI, 54.9.

EXAMPLE 27 Isodrin was prepared 'by reacting (2.2.1)-bicyclo-2,5-heptadiene with hexachlorocyclopentadiene. The adduct,

Cl QM.

melted at 101. An emulsion of 72.9 g. (0.2 mole) of this adduct in 200ml. pentane and 150 ml. water contain ing 0.4 mole hydrogen cyanide, 0.1mole sodium cyanide, and 0.5 g. Brij 30 was ozonized at 0 with 14.4 g.(0.3 mole) ozone. A mixture of 20 ml. concentrated hydrochloric acid and150 ml. ether was added; the ether layer was dried, and evaporated in aRotavapor evaporator at 65 and 0.2 mm., giving 81.4 g. viscous yellowproduct:

Analysis.-Calculated for C13H7NO2CIB (percent): C, 37.0; H, 1.7; N, 3.3;Cl, 50.2. Found (percent): C, 38.2; H, 2.4; N, 3.3; Cl, 49.4.

EXAMPLE 28 A mixture of 80.8 ml. (0.5 mole) hexachlorocyclopentadieneand 108 g. (1 mole) 1,5-cyclooctadiene was heated at for 14 hours, thendistilled, giving 42 g. unreacted cyclooctadiene and 57 g. of theadduct, hexachloronorbornylene-cyclooctene,

B, M.P. 63.

Analysis.-Calculated for C H C1 (percent): C, 41.0; H, 3.1; Cl, 55.9.Found (percent): C, 40.9; H, 3.3; Cl, 55.5.

The distillation residue, 53.1 g., was the adduct of 2 moleshexachlorocyclopentadiene with 1 mole cyclooctadiene.

A mixture of 19 g. (0.05 mole) of the hexachloronorbornylene-cycloocteneadduct in 150 ml. ether containing 0.4 mole hydrogen cyanide, and 4 g.sodium cyanide in 20 ml. water was ozonized at 10 With 4.8 g. (0.1 mole)ozone, Hydrochloric acid, 10 ml., was added; the ether layer wasevaporated, and the residue acetylated With 18.8 ml. (0.2 mole) aceticanhydride and 1 ml. concentrated hydrochloric acid. The mixture wasevaporated in vacuo; the residue, in ethanol, treated with charcoal,filtered, and evaporated, gave 17.5 g. of a viscous oil that had thestructure CI 1 Ab Ll CuJH -CH-CN Q! cu cg -cu-cu Analysis.Calculated forC H N O Cl (percent):

C, 41.4; H, 3.3; N, 5.1; Cl, 38.7. Found (percent): C, 41.2; H, 3.7; N,4.7; Cl, 38.6.

EXAMPLE 29 Dicyclopentadiene, 27.1 ml. (0.2 mole) was ozonized andacetylated according to Example 13. The product 8.6. g. could not bedistilled without decomposition except on a small scale. About 0.1 g.Was obtained boiling at 165-168 and 0.2 mm. having a mass spectrummolecular weight of 302 for the unresolved mixture of Analysis ofundistilled residue: Calculated tor C16H18N2O4 (percent): C, 63.6; H,6.0; N, 9.3. Found (percent): C, 64.4; H, 7.0; N, 8.8.

EXAMPLE 30 EXAMPLE 31 A solution of 112 g. (0.1 mole) of polypropylene(ave.

mol Wt. 1120; vis at 210 F., 800 SSU; 455 F. flash point) in 300 ml.hexane was cyanozanized according to Example 30, giving 111 g. ofwater-white viscous polypropylene cyanohydrin that contained 0.54% N andshowed the OH band at 3450 cm.- in the infrared.

EXAMPLE 32 A solution of 115.2 g. (0.2 mole) of polypropylene, (ave. molwt. 576) in hexane was cyanozonized according to Example 30. Evaporationin a Rotavapor evaporator left 118.5 g.- QI viscous white polypropylenecyanhydrin,

12 analyzing 81.0% C; 13.5% H; and 1.2% N; and showing the OH band at3450 cm." in the infrared.

EXAMPLE 3 3 A mixture of 115.2 g. (0.2 mole) light polypropylene (576ave. mol. wt.) in ml. hexane, 275 g. ether containing 1 mole hydrogencyanide and 3 ml. piperidine, 0.25 g. Brij 30, and 4 g. sodium hydroxidein 10 ml. water was ozonized at 510 with 24 g. (0.5 mole) ozone. Anadditional 0.2 mole hydrogen cyanide was added in ether, and the mixturestirred 1 hour at 20. It was acidified with 15 ml. concentratedhydrochloric acid. The ether-hexane layer was separated, and evaporatedin a Rotavapor evaporator, giving 127 g. of orange, viscous olypropylenecyanohydrin that analyzed 79.2% C; 13.1% H; and 2.6% N.

EXAMPLE 34 A mixture of 51.5 g. (0.02 mole) of polyisobutylene (ave.mol. wt. 2300, vis. 15,000 SSU at 210 F., 460 F. flash point) in 200 ml.pentane, ml. of ether containing 10.8 g. (0.4 mole) hydrogen cyanide,and 2 g. (0.04 mole) sodium cyanide in 4 ml. water was ozonized at 20with 9.6 g. (0.2 mole) ozone. After 4 ml. concentrated hydrochloric acidwas added to make the mixture acid, the ether-pentane solution wasfiltered from the sodium chloride, and evaporated on the steam bath togive 52.6 g. of yellow viscous high-molecular weight hydroxynitrileproduct that analyzed 83.9% C; 14.6% H; and 0.17% N.

20 g. of the hydroxynitrile product and 4 g. tetraethylenepentamine wereheated at 100 C. for 8 hours' in a bomb. The mixture was cooled,dissolved in pentane, filtered through Celite, and the clear pentanesolution was evaporated on the steam bath to give 20 g. of a clear,light orange alpha-aminonitrile product that analyzed 80.8% C; 13.6% H;and 1.8% N.

A 0.5 weight percent solution of this aminonitrile product in kerosenesuspended one g. of fine charcoal for 16 hours, whereas the samecharcoal suspension in kerosene without the product was completelysettled in 10 minutes.

EXAMPLE 3 5 A mixture of 40 g. of polyethylene grease (a polyethylene of2000 ave. mol. wt.) in 300 'ml. hexane, 21 ml. ether containing 0.3 molehydrogen cyanide, and 2 g. sodium cyanide in 4 ml. Water was ozonized at0 with 9.6 g. (0.2 mole) ozone. A one-quarter portion of the hexanemixture was withdrawn, and evaporated giving 10 g. of polyethylenecyanohydrin, analyzing 0.22% N.

The remainder of the mixture was heated with 20 ml. concentratedhydrochloric acid at 70 for 48 hours with stirring. The mixture wasdried, and evaporated, giving 29.1 g. of light brown, viscouspolyethylene alpha-hydroxy acid that analyzed 82.2% C; 13.9% H; and acidnumber 28.

The term cyanozonolysis has been coined to describe the one-step methodof this invention wherein the simultaneous reaction of an organiccompound containing at least one carbon to carbon double bond, hydrogencyanide, and ozone is effected either in the absence or presence ofammonia or an ammonia generating compound to form hydroxy-substituted oramono-substituted nitriles. The preferred method for isolatingcyanozonolysis products is to acetylate the crude ozonized reactionmixture, and then distill the acetylated mixture.

The foregoing examples thus illustrated that the process of thisinvention-cyanozonolysisprovides a simple and economical means forconverting, in one step, organic compounds containing at least onecarbon to carbon double bond into valuable derivatives. Obviously, manyvariations in reaction, and workup and conversion procedures can be usedto increase the versatility of the process. For example, volatile or lowboiling unsaturated com- 13 pounds can be treated in accordance with theinvention by the simultaneous introduction of separate streams of therespective reactants into the basic liquid reaction medium.

I claim:

1. The method of forming alpha-aminonitriles from organic compoundscontaining at least one non-aromatic carbon to carbon double bond whichcomprises: ozonizing at least one non-aromatic carbon to carbon doublebond of an organic compound containing at least one non-aromatic carbonto carbon double bond with ozone under basic liquid reaction conditionsin an inert liquid reaction medium containing at least two mob ofhydrogen cyanide per mol of said compound and at least one mol ofammonia per mol of said hydrogen cyanide.

References Cited UNITED STATES PATENTS 3,344,179 9/1967 Takahashi260-534 10 JAMES A. PATTEN, Primary Examiner US. Cl. X.R.

P0405) UNITED STATES PATENT OFFICE CERTIFIQA PE 01* CORREL 1011 PatentNo. 3,5 3,995 Dated March 31, 1970 Inventods) Ellis K. meme It iscertified that, error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

F" Column 3, lines 37-38, "2,9-dihydroxyaebacic" and line +9,"2,9-dihydrmy cebacic" should read 2,9-d1hydroxysebacic Column line 15,"2 15" should read 2 15 --5 line 63, after "acetic" insert acid Column5, line 26, after "32.8" insert g. line 62, the formula reading "0 11 30" should read C H N 0 Column 6, that portion of the formula, ling:

18 2h 2 I 1 3-9, reading H NCC-CH2- should read NC-C-CH2- Column 6, line25, the formula reading "C H H O" should read C that portion of theformula, lines 49-50, reading -CH=CH -CH -('Z'H-HC should read -CH-CH-CH-CH -(l)H-CH OAc 0A0 Column 7, that portion of the formula, lines 5-13,reading 25? should read 2 Column 7, that portion of the formula, lines27-35, reading CHQ-CHOH-CH H2-CH0H-CN should read CH2 c11 Column 9 thatportion of the equation, lines 10-13, reading c0oMe C3 should read-COOMe HCN O3 i(:Jlumn 12, line 6h, "amonm" should read amino- I SIGNEDAND snuzn BEAL) AM $EP291970 1 Edward M. Fletcher, Ir.

V I 2: Y JR. Mu; Officer 1 Comissioner of Patents

